2, 2&#39;, 4&#39;-tri-hydroxy benzophenone esters of dicarboxylic acids



United States Patent 3,366,668 2,2, -TRI-HYDROXY BENZOlPI-IENQNE ESTERS0F DICARBOXYLIC ACIDS Albert F. Strobel, Delmar, and Sigmund C. Catino,Castleton, N.Y., assignors to General Aniline & Film Corporation, NewYork, N.Y., a corporation of Delaware No Drawing. Continuation-impart ofapplication Ser. No. 129,246, Aug. 4, 1961. This application Oct. 23,1965, Ser. No. 504,154

Claims. (Cl. 260475) This application is a continuation-in-part ofapplication Ser. No. 129,246, filed Aug. 4, 1961, now abandoned.

This invention relates to new and useful ultra-violet absorbingcompounds, and to polymeric materials produced by the coreaction of suchultra-violet absorbers with polymer forming compounds and preformedpolymers, and in particular to derivatives of 2-hydroxybenzophenoneswhich are ultra-violet absorbing materials and which may be reacted withpolymers and polymer-forming reactants to form ultra-violet absorbingpolymeric absorbing substances and to the processes for producing suchcompounds and compositions.

Various organic compounds exhibit the power to absorb electromagneticradiations within the band of 2,900 to 3,700 A. and when incorporated invarious plastic materials such as transparent sheets, the resultantsheet acts as a filter for all of the radiation passing through and willtransmit only such radiations as are not absorbed by the sheet and/orthe absorbing agent. It is thus possible to screen out undesirableradiations and utilize the resulting transparent sheet as a filter inmany technical and commercial applications such as wrappings for foodproducts and the like.

Numerous organic compounds have been suggested as absorbents for therange of radiations described above, which range is designated as theultra-violet range. Such uses include incorporation in plastic sheetmaterials and the stabilization in general of tarnsparent plasticbodies. By far, the greatest concern with respect to ultra-violetradiations is with those radiations which come from the sun. Most ofthese radiations have wave lengths between 250 and 400 millimicrons. Theeffects of such radiation on the human skin, producing sunburn andsuntan, are of course well known. Other effects, however, of greatcommercial importance relate to the photochemical degradation caused byultra-violet radiations. Many commercial products are either unstablewhen subjected to such radiations, or are affected to the extent thatthey become undesirable or unsalable. Many plastic materials, whenexposed to this radiation, undergo substantial degradation resulting inthe development of undesirable color bodies and subsequent loss oftransparency. Food products, in addition to becoming discolored, oftenbecome unfit for human consumption. Thus, prolonged exposure of fruits,edible oils, butter and other prepared foods will cause them to spoiland turn rancid on exposure to ultra-violet light. It is well known thatcolored objects such as dyed textiles will fade on exposure to sunlight,and in particular to ultra-violet light. Many plastics, in addition todeveloping color formation and reduction in transparency, becomebrittle, lose their elasticity, crack and eventually completelydeteriorate on exposure to sunlight. Paints, varnishes, lacquers and thelike also are prone to these effects, even though here the transparencyproblem may not be paramount.

In most of the above applications, whether the ultraviolet absorbingmaterial is to be employed in a plastic film for protection thereof orin a film-forming composition to protect materials to be packaged insuch filmformers, or whether they are to be employed in paints,varnishes, lacquers and the like, or as an ingredient in Patented Jan.30, 1968 dyeing along with resinous auxiliaries, it has been commonpractice to intimately admix the ultra-violet absorbing material withthe film-forming substance to protect the film-forming material againstthe ultra-violet light. It had been early recognized, however, that oneof the major disadvantages of this technique was the tendency of theultra-violet absorbing compounds to leach out, migrate or volatilizefrom the film-forming material whereupon the compositions slowly becomemore and more susceptible to ultra-violet light degradation. It also hasbeen found that the effectiveness of any ultra-violet absorbing materialis related to the degree with which the said compound or material isdispersed throughout the carrier or film-forming material. Oftenadequate distribution and dispersion was difiicult, and the ultimate inprotection not forthcoming due to this lack of uniform distribution.

We have now discovered a clas of compounds which not only areoutstanding ultra-violet absorbers but are characterized by the presenceof functional reactive groups which are capable of coaction orinteraction with polymeric substances or polymer forming materials toyield.

polymeric amides or esters. Such reacted polymers containing a smallamount of ester and amide moieties with the ultra-violet absorbingcompound not only are characterized by the expected advantageousproperties of the polymer in its unmodified form, but the additionalcharacteristic of stabilization against ultra-violet radiation is nowafforded to such materials due to the presence of the ultra-violetabsorbing moiety chemically bonded to ester or amide, or carbon linkagesof the polymer material. In the previous techniques, Whereasultra-violet absorbing compounds were merely admixed with polymermaterials to effect a stabilization thereof, the amount of ultra-violetabsorbing agent employed would vary from about 0.1% to about 10% basedon the Weight of the polymer. With the compositions of the presentinvention, much less ultraviolet absorbing moieties are necessary toeffect the same degree of stabilization due to the greater deficiency inthe distribution thereof throughout the polymer material, and thus Whereheretofore 0.1% would effect a slight stabilization of a given polymer,in the instant case an exceptional degree of stabilization is achievedwith only slight amounts of ultra-violet absorbing moieties, especiallyafter long exposure to light. In general, the amount of the ultra-violetabsorbing compound to be chemically bonded to the polymer should rangefrom about 0.1% to about 5% based on the weight of the polymericmaterial.

It is therefore an object of the present invention to provide new anduseful compounds which are characterized by their outstandingultra-violet absorbing properties.

It is still another object of the present invention to provide new anduseful derivatives of 2,2'-dihydroxybenzophenones which are outstandingultra-violet absorbing compounds.

It is still a further object of the present invention to provide new anduseful 2,2'-dihydroxybenzophenone derivatives which are outsandingultra-violet absorbers and which are capable of further reaction to formester and/ or amide linkages with hydroxyl and/or amine groups.

It is still another object of the present invention to provide new anduseful derivatives of 2,2'-dihydroxybenzophenone which may be reactedwith polymerizable materials or pre-formed polymers to yield polymericcompositions which exhibit ultra-violet absorbing characteristics.

It is still another object of the present invention to provide processesfor the preparation of new and useful ultraviolet absorbing compoundswhich are derivatives of 2,2- dihydroxybenzophenone.

It is still another object of this invention to provide processes forthe preparation of polymeric materials which contain ultra-violetabsorbing moieties as an integral part J thereof, said ultra-violetabsorbing moieties being derived from 2,2-dihydroxybenzophenonecompounds.

Other objects will appear hereinafter as the description proceeds.

The ultra-violet absorbing compounds which are contemplated herein forreaction with the polymer forming ingredients hereinafter to bedescribed are characterized as ortho-ortho dihydroxybenzophenonecompounds which contain an ester grouping in one of the para positionsrelative to the keto group of the benzophenone compound. There may alsobe present in the other para position or in one of the ortho positions asimilar ester grouping or a different one, or an oxysubstituent, e.g.,alkoxy or substituted alkoxy wherein the alkyl moiety may contain one to40 carbon atoms. The ester grouping has the following chemicalconfiguration:

II o o I wherein R is the nucleus of a polycarboxylic acid such as adicarboxylic acid, tricarboxylic acid, tetracarboxylic acid and thelike, n is O or 1, and X is hydroxy, halogen, or oxy lower alkyl, e.g.,OCH OCH CH OCH and the like. The oxysubstituent which may be present inthe second para positions (i.e., para to the keto group) or in the orthopositions as pointed out above, may contain substituted alkyls. Theseinclude hydroxy alkyl, halo alkyl, alkoxy alkyl, hydroxy alkoxy alkyl,cyanoalkyl and the like, as well as aryloxy and substituted aryloxys. Inaddition, the benzene nuclei of the benzophenone compound may containother non-chromophoric substituents in the remaining free orunsubstituted positions. These include halogen, alkyl, cyano,substituted alkyl, e.g., hydroxyalkyl, cyano alkyl, haloalkyl and thelike; SO alkyl (e.g.,

-SO2CH2, -SO2CI-I and the like).

A generic structural representation of the above described group ofcompounds may be given as follows:

on 0H lRlt (lR Z /i /2 11 wherein (ARM and (AR) represent the monocycliccarbocyclic aromatic nuclei, i.e., benzene rings. The hydroxyl groupsare ortho-ortho with respect to the keto groups (i.e., vicinal thereto)and the Z group is the ester group: O?B(I%X 0 III wherein R representsthe moieties of a dior polycarboxylic acid radical and 11:0 or 1;

X represents hydroxyl, halogen (for example, chlorine or bromine), or 0Rwherein R is lower alkyl (i.e., 1 to 9 carbon atoms) or lowersubstituted alkyl;

Z may be hydrogen, hydroxyl, OOC(R),,COX (X as above), or OY (where Ymay be alkyl of from 1 to 40 carbon atoms, or an alkyl group substitutedby non-solubilizing groups: such non-solubilizing substituents in thealkyl radical may be halogen, hydroxyl, 0R CR and nitrile, R being loweralkyl and R lower alkylol, both of from 1 to about 9 carbon atoms);

P and Q may be any non-chromophore such as hydro- 4 gen, halogen, alkyl,alkenyl, alkoxy, alkaryl, or other substituted alkyls such as haloalkyl,hydroxyalkyl, cyanoalkyl and the like. P may also be oxy (as Z) when Zis hydrogen and conversely Z may be any of the P substituents when P isoxy.

The compounds encompassed by the above general Formulas III and IVcontain at least one functional grouping which is capable of forming anester or amide linkage with hydroxyl, amino or amido groups. In general,the procedure for forming the stabilized polymeric compositions of thepresent invention involves admixing the above described compounds withany polymerizable monomer or partially polymerized polymer or fullypolymerized polymer which contains hydroxyl, amino or arnido groups,either before or during polymerization of said polymerizable materialunder such conditions that an interaction between the compounds isproduced whereby esters and amides of the ultra-violet absorbingcompound and the polymer result through the usual processes ofesteriiication, transesterification and amidation.

The compounds of general Formula I are obtained by reacting aZ-hydroxybenzophenone compound with a dior polycarboxylic acid or amonoester or anhydride thereof in such a manner that one or both of the4-hydroxy groups of the Z-hydroxybenzophenone compound are esterified.The resulting product may be employed as such for interaction with thepolymer or polymer forming ingredients or may be converted and used asan ester or acid chloride.

It is, of course, understood that the dior polycarboxylic acidscontemplated, as illustrated below, includes oxalic acid and that, inthis instance, 12:0 and R does not exist.

The benzeophenone compounds of the Z-hydroxybenzophenone type which maybe employed as intermediates in the present invention include thefollowing:

2,2,4-trihydroxybenzophenone and the following substituted derivativesthereof:

3-allyl 5-allyl-3-methoxy 5 benzyl S-benzyl sulfonyl 3-bromo S-bromo6-brorno-5(1,3-dihydroxypropyl) 4-caproyl S-chloro 4-chloro S-chloro 3,5-dibromo 5 1,l-dibron1o-2,2-dichloro-l-cyanoethyl) 3,5-dichloro3,5-di-isopropyl 3 ,4-dimethoxy 4,5 -dimethoxy 3,5-dimethyl 4,5-dimethyl4,6-dimethyl 3-ethoxy 4-ethoxy S-ethyl G-ethyl 4-cyano 5 l-chloropropyl)5-chloro-4-methyl 5-bromo-4-rnethyl 3,5-dibrorno-4-methyl 5-ethyl-3-phenyl 4-cluoro 5 -isobutyryl 3-isopropyl B-methoxy 4-methoxy-methoxy 3-methoxy-5-propenyl 3-methyl 4-methyl S-methyl 6-methyl4-propoxy 4,5,6-trichloro 3,4,6-trimethyl, and the like.2,2,4,4'-tetrahydroxybenzophenone and the following substitutedderivatives thereof:

6-amyl 6-amyl-3,5-dibro-mo S-bromo 3,6-dimethyl 3-ethyl S-ethyl3-ethyl-5-isopropenyl 5-ethyl-3-methyl 6-heptyl 3-rnethyl S-methyl6-methyl 5-phenethyl 6-propyl 5-chloro-6-methyl 3,5-dichloro 6-pentyl3-bromo-5-ethyl 5-butyl 5-chlor0 S-hydroxyethyl 5-hexyl S-cyanoethyl5-chloroethyl 6-hydroxypropyl 6-chloropropyl 6-methoxyethyl VS-ethoxyethyl, and the like.

Many of the above described benzophenone comopunds are novel, and all ofthese new compounds may be prepared by the general processes describedin US. Patents 2,854,485 and 2,921,962. In these patents, methods aredescribed wherein an ortho-hydroxyarylcarboxylic acid is condensed witha selected phenol to yield the corresponding polyhydroxybenzophenoneemploying as a catalyst either a mixture of phosphorus oxychloride andzinc chloride in the presence of 85 to 98% phosphoric acid, or as thecatalyst system, a mixture of phosphorus trichloride and zinc chloridein the presence of phosphoric acid of strength 100 to 106%. In theexamples which follow below, there are illustrated various preparationsfor some of the novel benzophenone compounds above described.

The diand polybasic acids which may be used to 5 form the carboxylmoiety of general Formula I include the following:

6 u-chloro-a'-bromosuccinic chloro-methyl malonic a-chloro glutaric,G-bromo glutaric ethyl malonic a-ChlOlO ethyl malonic a-bromo ethylmalonic y-bromo ethyl malonic u,'y-dibromo ethyl malonic [3,,8-dichloroadipic a-bromo adipic j8-bromo adipic oz,oz'-dibf0m0 adipicB,,8'-dibromo adipic a-methyl glutaric ,B-brorno-a-methyl glutarica-bromo-u-methyl glutaric propyl malonic [fl-bromo-propyl] malonicB-bromo-fi-methyl glutaric methyl ethyl malonic isopropyl malonic butylmalonic rat-methyl adipic p-ethyl glutaric methyl propyl malonicisobutyl malonic 3,}3-dimethyl glutaric diethyl malonic a,a'-dib1'0m0suberic a, x-dimethyl adipic a,ot-dimethyl adipic u,a'-dib1'0m0 azelaica,a-dibromo sebacic n-heptyl malonic tetradecyl malonic eicosyl malonicdicetyl malic dichloromaleic bromomaleic glutaconic itaconic chloroconicmethyl maleic (citraconic) ethylidene malonic hexene-Z-dicarboxylic aciddihydromuconic a-methyl glutaconic 'y-methyl itaconic ethyl citraconic'y-isobutyl it-aconic fi'-methyl-a-allyl adipica-isoamyl-o'-isoamylidene glutaric 2-al1yl adipic hexyl-allyl malonictetradecyl maleic 12,15-dimethyl-docosene (1,2)-dicarboxylic acid (1,1)eicosene (8)-dicarboxylic acid (1,20) cyclopropane dicarboxylic acid(1,2) cyclobutane dicarboxylic acid (1,2) 1,2-dibromo cyclobutanedicarboxylic acid (1,2) cyclobutane dicarboxylic acid (1,3) 3-methylcyclopropane dicarboxylic acid (1,2) cyclopentane dicarboxylic acid(1,2) cyclopentane dicarboxylic acid (1,3) 1,2-dimethylpentanedicarboxylic acid (1,2) 1,1-dimethylpentane dicarboxylic acid (2,3)cyclohexane dicarboxylic acid (1,2) cyclohexane dicarboxylic acid (1,3)2-bromohexane dicarboxylic acid (1,3) cyclohexane dicarboxylic acid(1,4) l-bromohexane dicarboxylic acid (1,4) 1,2-dibromohexanedicarboxylic acid 1,4) cyclopentyl malonic acid cyclohexyl malonic acid1,2-dirnethy1 cyclopentane dicarboxyiic acid (1,3)cyc1obutene-(1)-dicarboxy1ic acid (1,2) cyc10pentene-(1)-dicarboxy1icacid (1,2) cyc10heXene-(1)-dicarb0xy1ic acid (1,2)cyc1ohexene-(2)-dicarboXy1ic acid (1,2) cyc10hexene-(4)-dicarb0xy1icacid (1,2) cyciohexene- (4) -dicarboxylic acid (1,3)cyc10hexene-(2)-dicarb0xy1ic acid (1,4) syrnm. spiroheptane-dicarboxylicacid cyclohexadiene-(2,4)-dicarb0xylic acid (1,2)cyc1ohexadiene-(1,4)-dicarb0xy1ic acid (1,4) phthaiic isophthalicterephthalic 3-ch1orophtha1ic 4-ch1orophtha1ic 3,4-dich1or0phtha1ic3,5-dichlorophthalic 3,6-dichlorophthalic 3,4,5-trich1orophtha1ictetrachlorophthalic 3-bro1nophtha1ic 4-bromophtha1ic5-ch1or0-4-brom0-phtha1ic 3,5-dich1or0-4-bromo-phthaiic 3-i0d0 phthalic4-i0d0 phthalic 4-ch1oro isophthalic 4,6-dich10r0 isophthaiic2,4,6-ti'ich1oro isophthaiic 4 br0rno isophthalic 4,6-dibrornoisophthalic terephthalic 3-su1farny1 phthalic 4-su1farny1 phthalic2,5-dich10r0 terephthaiic 5-c111or0-2-brorno terephthaiic 2,5-dibr0motercphthalic phenyl malonic Z-carboxyi-phenyl acetic S-rnethyl phthaiic2-methy1 isophthalic 4-methy1 phthalic 4-methy1 isophthalic S-rnethylisophthalic benzyl malonic o-phenylene diacetic p-phenylene diaceticoc-b6flZYi gintaric B-benzyl glutaric 8,p-to1y1 glutarico-xylylendiacetic m-methyl-fi-phenyl glutaric S-tert. butyl-isopht-halictetrarnethyl phthalic a-methyl-d-benzyl glutaric phenyl maleic benzalmalonic 2-ch1or0 benzal malonic 2-brorno benzal malonic -phenyl itaconicphenyl cittaconic B-phenyl glutaconic 2-rnethy1 benzal malonic 3-pheny1cyclopropane dicarboxylic acid (1,2) cinnarnyl malonic fl-benzalglutaric 4-isopr0py1 benzal malonic benzal glutaconic naphthalenedicarboxylic acid (1,8) naphthalene dicarboxylic acid (1,4) naphthalenedicarboxylic acid (1,5) naphtha1ene dicarboxylic acid (2,7) diphenyldicarboxylic acid (2,2 [diphenic] 4-ch1oropheny1 dicarboxylic acid(2,2')

4-bromopheny1 dicarboxylic acid (2,2) S-bromophenyl dicarboxylic acid(2,2') 4,4-dibrorn0pheny1 dicarboxylic acid (2,2') diphenyl dicarboxylicacid (2,3') diphenyl dicarboxylic acid (2,4) diphenyl dicarboxyiic acid(3,5 diphenyl dicarboxylic acid (3,3) diphenyl dicarboxylic acid (4,4')diphenyi malonic diphenyl maleic cyc1opropane tricarboxylic (1,2,3)cyc10pentane tricanboxylic (1,2,4) tricarba11y1ic[1,2,3-propanetricarboxylic] benzene tricarboxylic (1,2,3)[hemirne11itic] benzenetricarboxy1ic( 1,3,5) [trimesic] benzene tricarboxy1ic( 1,2,4)[trimeliitic] 4,6-dich1oro hemirne11itic S-sulfamyl trimellitic diphenyltricarboXyiic acid (2,3,4) diphenyl tricarboxylic acid (2,4,3')pyromellitic (1,2,4,5-benzene tetracarboxylic acid) 3,5-dicarboxy phenylacetic malic citric tetrahydrofurane dicarboxylic acid (2,5)tetrahydropyrane dicarboxyiic acid (4,4) 2,2,6-trimethy1tetrahydropyrane dicarboxylic acid (3,6) 2-rnethy1-5-is0propy1tetrahydrofurane dicarboxylic acid (2,5) 2,3-dihydrofuran dicarboxylicacid (2,5) 2,5-dihydr0furan dicarboxylic acid (2,5) furane dicarboxylicacid (2,5 2,5-dirnethy1 furane dicarboxylic acid 3,4) furan-di(p-propionic acid) (2,5) 3,4-dipheny1ene thiophene dicarboxylic acid(2,5) 4,5-rnethy1ene dioxy phthalic pyrrolidine dicarboxylic acid (2,2)pyrrolidine dicarboxylic acid (2,5) N-pheny1 pyrrolidine dicarboxylicacid (2,5 piperidine dicarboxylic acid (2,3) piperidine dicarboxylicacid (2,6) piperidine dicarboxylic acid (3,4) N-methyl piperidinedicarboxylic acid 2,6) pyrrolidine a-carboxylic acid-u'-acetic acid3-rnethy1 pyrrolidine dicarboxylic acid (2,5) pyrrole dicarboXylic acid(2,5 N-ethyl pyrrole dicarboxylic acid (2,5) N-phenyl pyrroledicarboxyiic acid (2,5) 3,4-dibr0mo pyrrole dicarboxylic acid (2,5)3,5-dirnethy1 pyrrole dicarboxyiic acid (2,4) 1-pheny1-2,5-din1ethy1pyrrole dicarboxylic acid (3,4) pyrridine dicarboxylic acid (2,3)pyridine dicarboxyiic acid (2,4) S-bromo pyridine dicarboxylic acid(2,3) pyridine dicarboxylic acid (2,6) 4-ch1or0pyridine dicarboxylicacid (2,6) 2,6-dich1oro pyridine dicarboxyiic acid (3,5) 4-ethy1pyridine dicarboxyiic acid (3,5) 4-methy1-5-ethy1 pyridine dicarboxyiicacid (2,3) quinoiine dicarboxylic acid (2,3) quinoline dicarboxylic acid(2,4) 2-1nethy1 quinoline dicarboxylic acid (3,4) 4-pheny1 pyridinedicarboxylic acid (3,5 S-methyl pyrrole tricarboxylic acid (2,3,4)2,4,6-pyridine tricarboxylic acid (trimesitic) pyrazole dicarboxylicacid (3,4) 1-pheny1 pyrazole dicarboxylic acid (3,4) imidazoledicarboxylic acid (4,5) 4-1nethy1 pyrazole dicarboxylic acid (3,5)pyrimidine dicarboxylic acid (4,5 benzimidazole dicarboxylic acid (2,4)quinoxaline dicarboxylic acid (2,3) 5'methy1 isoxazole dicarboxyiic acid(3,4) 2-rnethy1 thiazole dicarboxylic acid (4,5)

and the like and their anhydrides and acid chlorides. (12) OH OH Asindicated above, the prepared acid derivatives may I be used as such inthe free acid form and the esters, or they may be converted to acidhalides, for example, acid II I I chlorides and bromides, and used inthis form. 0 Br Br The following exemplify some of the specific com- 3)o H 0 H I elcosyl pounds within the general Formula I above:

moo-Q-o 0- o O-CHCO 0H 1 on OH I 14 H O HO -oo oooomomooon 2 on onHo-oo-0000H;0H;0ooolh (15) H H on OH HO -oo ococmomoooi ll H (ll-C0011 OOG-H 16 OH OH (5) H 0H I 1 c1 oo- 01 moo-Q-ooQoooomcmoocr H300 Q 00 Q gQ 01 OOOH 0 0H (6) $11 In; .(18) I H I (30011 SOzNHz (7 OH OH 0Ha I I OHOH I I HOOO oo coon 00011 N H (8) OH OH 5 i mooocmm-oooo o0-OCO?OH2COOCH3 OH OH (9 nt H0 (20) N GO o0o0H=oH-o00H OH H H000- 1-10-0-oo 00 (10 OH OH Q I i l mo 6 N Q I? 0 COOH A general method of preparingsuch esters of 2-hy- 7 droxybenzophenone and dior poly-carborylic acidsis (11) OH OH as follows: the ultra-violet absorber is dissolved in aslightly alkaline (pH 8-9) aqueous solution and maintained at that pHduring the addition of an acid anhyoo OOCH- HCOOH Q Q II I G 2 dride oracid chloride of the dlor poly-carboxylic acids. 0 C1 7 The temperatureof the reaction may be carried out at from about room temperature toreflux, but preferably at room temperature to about 70 C. To prepare themonoester, it is necessary to use one mole of hydroxybenzophenonecompound per one mole of acid anhydride or acid chloride, although inpractice it is customary to use an excess of acid anhydride or acidchloride, up to 100% excess due to the possibility of accompanyinghydrolysis of the acid anhydride or chloride in the aqueous alkalinesolution during esterification. Likewise if a diester is to be produced,a minimum of two moles acid anhydride or acid chloride per one mole ofhydroxybenzophenone compound is required, but in practice excess acidanhydride or acid chloride is employed. In carrying out theesterification, it is predominantly the 4 and 4'-hydroxysubstituentsthat are esterified, although the final products may contain otherisomers, unreacted material and the like. For example, if2,2-4,4-tetrahydroxybenzophenone is esterified with a slight excess overone mole of succinic anhydride, there results predominantly OH on I lITO-Q-CO-QOCOCEROHZCOOH although there may be some of the product OH OHOCOCH2CH2COOII nooomomooco -od together with minor amounts ofZ-esterified compounds and some of the initial reactants. Such a mixturemay be employed as a co-polymerizable ultra-violet absorber, or themixture may be separated into its components and only the effectiveultra-violet absorbing components employed.

In reacting the above compounds with polymerizable compositions orpreferred polymers, the acid derivatives per se, or the acid derivativesconverted in known manner to acid chlorides or carbalkoxy derivativesare added to the polymerizable equivalent of, for example, 2,2,4-trihydroxybenzophenone with 3 equivalents of pyridine in benzene,cooling and adding 1.2 equivalents of the acid chloride of thecarboxylic compound. Thus 1 equivalent and 3 equivalents of pyridine inbenzene is stirred and cooled to 5 C. There is added dropwise over aperiod of 1 hour 1.2 equivalents of HOOC--CH COCl (Beilstein II, p. 582)After a few minutes the solution is washed first with water, then diluteHCl, and finally saturated Na CO solution. The benzene is evaporatedunder reduced pressure to yield crude OH I10 I I I 6]) As an alternativethe ultra-violet agent may be added to the polymerizable composition indispersed form.

The polymerizable compositions include solutions or melts of monomers,partially polymerized polymers, or preferred polymers which contain freehydroxy or phenolic groups and amine groups as illustrated by thefollowing:

(1) alkyd resin forming compositions as illustrated by dibasic acids andpolyalcohols, e.g., phthalic acid and glycol or glycerol;

(2) phenol-formaldehyde resin forming compositions;

(3) melamine-formaldehyde resin forming composi.-- tions;

(4) nylon type resin forming compositions;

(5) amine-formaldehyde resin forming compositions. such as aniline andformaldehyde;

(6) unsaturated compounds as, for instance, styrene= or maleic oracrylic monomers or polymers.

In addition to the use of such compounds as additives which react inresin forming compositions, it is to be understood that the compoundsper se may be employed as one component of a polymerizable composition.

The following examples will serve to illustrate the present inventionwhereby compounds of general Formula I are prepared as Well as theapplication thereof in polymer materials. These examples are not to beconsidered limitative of the present invention. Where parts arespecified these are to be interpreted as parts by weight unlessotherwise indicated.

EXAMPLE 1 Preparation of:

OH HO I 0 I Into a dry 500 cc. flask fitted with a stirrer, thermometer,reflux condenser, drying tube and heating mantle there are charged 52.8gm. of 2,2-4-trihydroxy-4'-methoxy benzophenone (0.16 mol, M.W.=264:%)and 150 ml. of dry picoline. At room temperature 16.0 gm. of succinicanhydride is added gradually, keeping the temperature below 60 C. Thematerial is held 1 hour at 60 C., then drowned into 500 ml. water at10-15' C., and acidified to Congo grey with ml. acetic acid. The wateris decanted at 5 C. The oil is re-slurried in 500 cc. Water, the pHadjusted to Congo grey with glacial acetic acid; water is decanted at 5C., and oil is re-slurried in 500 cc. water which is decanted at 5 C.The oil is then dissolved in 500 cc. benzene, nuchared (treatment withactivated carbon) and filtered, then the henzene is evaporated. Dried inair, the yield is 44 gm. of crude product. The material isrecrystallized to give the desired product having the formula 0 H HOApplication of the product to a styrene-polyester resin is carried outas follows: 1 mole phthalic anhydride, 1 mole succinic anhydride, 2moles diethylene glycol and 0.214% of above prepared ultra-violet agentare reacted and diluted to 60% solids with styrene. The finished productis cured in a mold, then exposed in a fadeometer for 100 hours. Thematerial so prepared is distinctly better than the product prepared byfirst forming the polymer, and later adding the same percentage ofultra-violet absorber, and milling it until homogeneous.

The 2,2,4-trihydroxy-4-methoxybenzophenone may be prepared in the mannerdescribed'in Example VIII of US. Patent 2,921,962.

EXAMPLE 2 Preparation and application to polyester of:

OH HO I I O o oo COOH

of total weight of the above resin-forming reactants of:

The mixture is heated at 160 C. for 3 hours. This polymerized mixture isfaster to light and heat in the fadeometer after 100 hours than asimilar mixture free from U the 2-hydroxybenzophenone compound. In thesame way when the above absorber is added to the finished polymer afterpolymerizing the plastic, and then milling until homogeneous (beforecomplete polymerization has occurred), a final product of less fastnessto heat and light is obtained.

EXAMPLE 3 Preparation of This compound is prepared in the same manner asthe absorber of Example 1, substituting an equirnolar amount of forbenzophenone starting compound of that example and an equirnolar amountof oxalyl chloride, for the succinic anhydride used in Example 1. Theproduct is used in polyester resin exactly as the compound of Ex ample1.

EXAMPLE 4 Preparation of:

and application to melamine-formaldehyde resin Preparation of:

on no t r t @d-Q-oo-omom-d-or is carried out by refluxing 1 mole of onno u i Q-o-Q-oo-otmlmooon with a twofold weight excess of thionylchloride for 3 14 hours, then distilling the excess thionyl chloride toleave an essentially dry product. The crude product is formula:

OH HO is used as such in melamine-formaldehyde resin.

The condensation between 1 molar equivalent of rnel amine and 2 /2 molarequivalents of formaldehyde is carried out at C. using aqueousformaldehyde (40%) and partial vacuum. Comparison between resinpolymerized using 1% (based on total weight of plastic solids) of OH HOi i @O-QO o omorno 0 or with resin free from ultra-violet absorber showsgreater light stability in the resin copolymerized with the absorber.

EXAMPLE 5 Another method of accomplishing the same essential result asin Example 4 is to treat one mole of on no r' O @d-QoJi-omom-o-or with 1mole of melamine to give the product of the formula:

The latter compound at 1% concentration is then mixed withmelamine-formaldehyde and copolymerized exactly as in Example 4.

EXAMPLE 6 in polyester. This is prepared as in Example 1, using anequivalent amount of 2,2',4,4 tetrahydroxy benzophenone and 32 g. ofsuccinic anhydride.

EXAMPLE 7 In place of the ultra-violet absorbing compound of Example 1,an equirnolar quantity of OH H0 is reacted with succinic anhydride.Application to resin as in Example 1 results in a product havingimproved ultra-violet properties over a similar resin prepared withoutthe ultra-violet agent.

EXAMPLE 8 In place of the ultra-violet absorbing compound of Example 2,an equirnolar amount of 6 Ha6ilw :15 reacted with two equimolar amountsof phthalic an- 'hydride. There results a product of the formula:

00011 000151 which, when employed in resin formation in the manner ofExample 2 results in the production of a resin having improvedultra-violet properties.

EXAMPLE. 9

Preparation of:

H H o A. Preparation of 2,2,4'-trihydroxy-3-vinylbenzophe- Inone:

are stirred together at C. until a uniform slurry is formed. Over a twohour period 38 g. of phosphorous trichloride is added and thetemperature during this addition rises to about C. The temperature isthen raised at the rate of about 5 degrees per hour for 4 hours until atemperature of 55-60 C. is reached. This temperature is maintained for16 hours, after which the charge is drowned in several liters of ice andwater, filtered and washed with cold 5% aqueous sodium bicarbonatesolution. The charge is then dissolved in hot water made slightly acidwith HCl, treated with Nuchar (activated carbon) and a very small amountof zinc, dust, filtered, cooled and crystallized and filtered. g. of2,2,4'-trihydroxy-3-vinylbenzophenone is obtained.

B. Example 1 is now repeated employing, however, in lieu of the 4methoxy derivative of that example an equivalent weight of the 3 vinylcompound prepared in A.

C. The product produced in B above is incorporated into a polyesterresin as in Example 1, and yields a well stabilized product.

EXAMPLE 10 Preparation of:

EXAMPLE 11 Preparation of:

H H o o I 0 l (I? ;o o CHflCHflCOCH l f E C 112- A. Preparation of 5benzylsulfonyl 2,2'4' trihydroxy benzophenone. This compound is preparedin a manner similar to the 3 vinylbenzophenone described above exceptthat 5 benzylsulfony]. salicylic acid in equivalent amounts is employedin lieu of the 3 vinyl derivative.

B. Example 1 is again repeated except that the above prepared 5benzylsulfonyl derivative in equivalent amounts is employed in lieu ofthe 4 methoxy compound of Example 1.

EXAMPLE 12 Preparation of:

A. Preparation of 5-hydroxyethyl-2,2,4,4-tetrahydroxy benzophenone.Example 2 of U.S. Patent 2,921,962 is repeated except that in lieu offi-resorcylic acid, an equivalent weight of the S-hydroxyethylderivative thereof is used.

B. Example 1 above is again repeated employing, however, a mole ratio ofsuccinic anhydride to the compound of A above of 2:1, thereby to yieldthe di-ester.

EXAMPLE 13 Preparation of:

H H O O i ii i l l C0011 CHzCHzCHzCl OOOH A. Preparation of6-chloropropyl 2,2',4,4' tetrahydroxy-benzophenone. Part A of Example 12above is repeated except that the 6-chloropropyl derivative is employedin lieu of the S-hydroxy-ethyl derivative.

B. Example 8 above is repeated again employing 2 moles of phthalicanhydride per mole of the benzophenone compound.

EXAMPLE 14 Preperation of is carried out as in Example 1, substitutingan equimolecular amount of maleic anhydride for the succinic anhydrideof Example 1.

Application of this compound to styrene-maleic anhydride copolymer iscarried out as follows:

A mixture is made of A gm. of the above absorber and gms. of Polylite8000 1 containing 1 gm. of Luperco ATC (50% benzoyl peroxide). A castingis made between glass plates treated with mold release agent (Dri-FilmSC-87). Gasket material is used between the plates; they are pressedtogether and the final copolymerization is carried out by raising thetemperature to 90 C., holding for 1 hour, raising to C., curing for /2hour. In this technique a copolymer is made wherein the ultravioletabsorber is cross-linked with the polymer by means of the double bondsof each. The light-fastness of the plastic containing the ultra-violetabsorber is far superior to the plastic made up without ultra-violetabsorber, and

Polylite 8000 is an unsaturated ester polymer manufae tured by RelcholdChemicals consisting of styrene-maleic anhydride-.phthalicanhydride-ethylene g2 ycol.

even superior to the plastic made up with an equal molar amount of inplace of the copolymerizable absorber shown above.

EXAMPLE 15 Preparation of:

is carried out in the same manner as in Example 14. Application inPolylite 8000 is carried out as in Example 14.

EXAMPLE 16 Example 1 is repeated employing as the benzophenone thefollowing compounds:

(LHzOHzQ OH OH O -Q Q- CHaCHaOCHa OH OH CHaCHzCN EXAMPLE 17 R O I R I Xin a para position and in the other ring not more than one oxysubstituent selected from hydroxy, lower alkoxy, and radicals of theformula:

in a para position; R is the nucleus of a polycarboxylic acid selectedfrom succinic acid, phthalic acid and halogen and lower alkylsubstituted derivatives thereof; X is a radical selected from the groupconsisting of hydr'oxy, halogen an CR and R is a lower alkyl radical offrom 1 to 9 carbon atoms.

2. 2,2'-dihydroxybenzophenone containing in the 4,4- positions a groupof the formula:

6 tI R 6' X R is the nucleus of a polycarboxylic acid selected fromsuccinic acid, phthalic acid, and halogen and lower alkyl substitutedderivatives thereof; each X is a radical independently selected from thegroup consisting of hydroxy, halogen, and OR, and wherein R is a loweralkyl radical of from 1 to 9 carbon atoms.

3. Compound of the formula:

OH no I I g H3O O-GdQ-O o-omo-o onmo 4. Compound of the formula:

5. Compound of the formula:

6. Compound of the formula:

7. Compound of the formula:

8. Compound of the formula:

9. Compound of the formula:

H H no 0 o I I f I (H) d oo-omomooon 10. Compound of the formula:

References Cited UNITED STATES PATENTS 3,072,602 1/1963 Clark et al260-45.85

LORRAINE A. WEINBERGER, Primary Examiner. R. K. JACKSON, Examiner.

T. L. GALLOWAY, Assistant Examiner.

1. 2,2''-DIHYDROXYBENZOPHENONE CONTAINING IN ONE RING A GROUP OF THEFORMULA: